Chemical Reviews,
Год журнала:
2023,
Номер
123(17), С. 10641 - 10727
Опубликована: Авг. 28, 2023
Enantiomers,
where
chirality
arises
from
restricted
rotation
around
a
single
bond,
are
atropisomers.
Due
to
the
unique
nature
of
origins
their
chirality,
synthetic
strategies
access
these
compounds
in
an
enantioselective
manner
differ
those
used
prepare
enantioenriched
containing
point
arising
unsymmetrically
substituted
carbon
center.
In
particular
stereodynamic
transformations,
such
as
dynamic
kinetic
resolutions,
thermodynamic
and
deracemizations,
which
rely
on
ability
racemize
or
interconvert
enantiomers,
promising
set
transformations
optically
pure
late
stage
sequence.
Translation
approaches
with
atropisomers
requires
expanded
toolbox
for
epimerization/racemization
provides
opportunity
develop
new
conceptual
framework
synthesis
compounds.
Nature Communications,
Год журнала:
2022,
Номер
13(1)
Опубликована: Фев. 28, 2022
Abstract
Biaryl
scaffolds
are
found
in
natural
products
and
drug
molecules
exhibit
a
wide
range
of
biological
activities.
In
past
decade,
the
transition
metal-catalyzed
C–H
arylation
reaction
came
out
as
an
effective
tool
for
construction
biaryl
motifs.
However,
traditional
reactions
have
limitations
like
harsh
conditions,
narrow
substrate
scope,
use
additives
etc.
therefore
encouraged
synthetic
chemists
to
look
alternate
greener
approaches.
This
review
aims
draw
general
overview
on
bond
formation
C–C
bonds
with
aid
different
methodologies,
majorly
highlighting
sustainable
Journal of the American Chemical Society,
Год журнала:
2022,
Номер
144(13), С. 6040 - 6049
Опубликована: Март 24, 2022
Axially
chiral
biaryls
and
heterobiaryls
constitute
the
most
represented
subclass
of
atropisomers
with
prevalence
in
natural
products,
bioactive
compounds,
privileged
ligand/catalysts,
optically
pure
materials.
Despite
many
ionic
protocols
for
their
construction,
radical-based
variants
represent
another
highly
desirable
intriguing
strategy
but
are
far
less
developed.
Moreover,
efficient
synthesis
axially
heterobiaryl
molecules,
especially
ones
having
multiple
heteroatoms
other
types
elements,
through
radical
routes
remains
extremely
limited.
We
herein
disclose
first
catalytic
asymmetric,
metal-free
construction
centrally
by
Minisci
reaction
5-arylpyrimidines
α-amino
acid-derived
redox-active
esters.
This
is
enabled
use
4CzIPN
as
an
organic
photoredox
catalyst
conjunction
a
phosphoric
acid
catalyst.
The
achieved
variety
interesting
featuring
union
α-branched
amine
generally
excellent
regio-,
diastereo-,
enantioselectivity
(up
to
82%
yield;
>19:1
dr;
>99%
ee).
finding
also
builds
up
new
platform
development
desymmetrization
methods
via
radical-involved
atroposelective
functionalization
at
heteroarene
prochiral
heterobiaryls.
Journal of the American Chemical Society,
Год журнала:
2023,
Номер
145(14), С. 7983 - 7991
Опубликована: Март 28, 2023
Conjugate
addition
is
among
the
most
important
synthetic
protocols
for
constructing
carbon
skeletons
and
widely
used
to
synthesize
natural
products
drugs.
However,
asymmetric
catalysis
studies
have
mainly
focused
on
stereogenic
centers
arising
from
conjugate
alkenes.
Here,
we
report
first
photoinduced
cobalt-catalyzed
dynamic
kinetic
reductive
reaction
that
enables
formation
of
heterobiaryls
with
axial
chirality
(45
examples,
up
91%
yield
97%
ee).
This
method
features
mild
conditions,
good
functional-group
tolerance,
excellent
enantiomeric
control.
Significantly,
large
amounts
metal
waste
precious
catalysts
can
be
avoided
under
these
conditions.
Migration
chiral
arylcobalt
species
into
alkene
might
rate-determining
step
based
studies.
Chemical Reviews,
Год журнала:
2023,
Номер
123(17), С. 10641 - 10727
Опубликована: Авг. 28, 2023
Enantiomers,
where
chirality
arises
from
restricted
rotation
around
a
single
bond,
are
atropisomers.
Due
to
the
unique
nature
of
origins
their
chirality,
synthetic
strategies
access
these
compounds
in
an
enantioselective
manner
differ
those
used
prepare
enantioenriched
containing
point
arising
unsymmetrically
substituted
carbon
center.
In
particular
stereodynamic
transformations,
such
as
dynamic
kinetic
resolutions,
thermodynamic
and
deracemizations,
which
rely
on
ability
racemize
or
interconvert
enantiomers,
promising
set
transformations
optically
pure
late
stage
sequence.
Translation
approaches
with
atropisomers
requires
expanded
toolbox
for
epimerization/racemization
provides
opportunity
develop
new
conceptual
framework
synthesis
compounds.
